WO2000034359A1 - Agents antichocs a base de caoutchouc de silicone polymerise en emulsion, procede de fabrication et melanges de ces agents - Google Patents

Agents antichocs a base de caoutchouc de silicone polymerise en emulsion, procede de fabrication et melanges de ces agents Download PDF

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Publication number
WO2000034359A1
WO2000034359A1 PCT/US1999/022870 US9922870W WO0034359A1 WO 2000034359 A1 WO2000034359 A1 WO 2000034359A1 US 9922870 W US9922870 W US 9922870W WO 0034359 A1 WO0034359 A1 WO 0034359A1
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WO
WIPO (PCT)
Prior art keywords
silicone rubber
weight
accordance
graft copolymer
thermoplastic
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Application number
PCT/US1999/022870
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English (en)
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WO2000034359A9 (fr
Inventor
Daniel Horace Craig
Rong Hu
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General Electric Company
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Publication date
Application filed by General Electric Company filed Critical General Electric Company
Priority to JP2000586800A priority Critical patent/JP2002531654A/ja
Priority to DE69938462T priority patent/DE69938462T2/de
Priority to EP99954707A priority patent/EP1141093B1/fr
Publication of WO2000034359A1 publication Critical patent/WO2000034359A1/fr
Publication of WO2000034359A9 publication Critical patent/WO2000034359A9/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes

Definitions

  • the present invention relates to silicone rubber-based impact modifiers in the form of polymerized alkenyl monomer-containing grafts, such as styrene and acrylonitrile, of emulsion polymerized silicone rubber particles having an average particle size in the range of about 400 nm or more. More particularly, the - present invention relates to the employment of such polymerized alkenyl containing impact modifiers in thermoplastic resins to provide thermoplastic compositions having enhanced impact strength and improved weatherability.
  • aqueous dispersions of organopolysiloxanes are provided in the form of monomodal organopolysiloxane particles having a pre-determined particle size of up to about 2 microns.
  • current manufacturing practices for making organopolysiloxane dispersions often emulsify pre-existing organopolysiloxane fluids or gums under high shear conditions.
  • Alternative procedures include batch stirring siloxane precursors in water in the presence of a surfactant.
  • Additional emulsion polymerization methods are taught, such as shown in U.S. patent 2,891,920, which describes the use of a base catalyst with a cationic surfactant, and
  • J.P.62141029 A2 870624 which is directed to a continuous addition of a pre- emulsion cyclo-siloxane precursor.
  • thermoplastic compositions comprising a thermoplastic polymer and an effective amount of an impact modifier in the form of a polymerized alkenyl monomer-containing graft of an emulsion polymerized silicone rubber having an average particle size of 400 nm, or greater.
  • the present invention is based on the discovery that silicone rubber particles having a volume average particle size of 400 nm or greater can be made by a single stage semi-continuous process involving the emulsion polymerization of siloxane precursors under low shear, substantially non- homogenizing conditions.
  • the expression “semi-continuous process” means the introduction under emulsion polymerization conditions of silicone rubber siloxane precursors, such as octamethylcyclotetrasiloxane and ⁇ - mercaptopropyltrimethoxysilane into a reactor over an extended period of time, for example, about 2 to about 12 hours, and preferably, about 4 to about 8 hours.
  • the expression semi-continuous process also includes the employment of mild, and/ or low shear non-homogenizing conditions during the emulsion polymerization of the silicone rubber siloxane precursors.
  • the degree of agitation used during the semi-continuous processing of the silicone rubber siloxane precursors substantially minimizes the formation of silicone rubber particles having an average particle size of below about 400 nm.
  • the resulting silicone rubber particles can thereafter be respectively grafted with a polymerizable alkenyl monomer, such as a vinyl monomer, to form a polymerized alkenyl polymer shell, to provide valuable impact modifiers for a variety of thermoplastic polymers, such as polyesters, polycarbonates, polyestercarbonates, polyimides, polyetherimides, and polyamides.
  • a polymerizable alkenyl monomer such as a vinyl monomer
  • a method for making an aqueous silicone rubber latex which comprises,
  • thermoplastic blend comprising (C), thermoplastic polymer and (D) about 5 % to about 50% by weight, based on the weight of therm * >pl st ⁇ c blend, of a silicone rubber graft copolymer having about 15% to about " ' , bv weight of alkenyl polymer shell, and silicone rubber particles ⁇ >lume average particle size in the range of about 400nm to about 2 n ⁇ r.
  • Still another aspect of the present invention is directed to a method for preparing a thermoplastic blend, which comprises mixing ( C ), thermoplastic polymer, and (D) about 5 % to about 50% by weight, based on the weight of thermoplastic blend, of a silicone rubber graft copolymer having about 15% to about 75% by weight of alkenyl polymer shell, and silicone rubber particles having a volume average particle size in the range of about 400nm to about 2 microns.
  • an emulsion polymerized silicone rubber latex is initially formed by semi-continuously adding to a reactor containing water, which is being agitated, such as by stirring, at a temperature in the range of about 30°C to about 110°C, and preferably about 75°C to about 95°C, a mixture of silicone rubber monomers.
  • the semi-continuous addition of monomers can be effected, stepwise, and in a dropwise manner, over a period of up to about 24 hours.
  • An effective amount of a surfactant can be used initially in the reactor as part of the agitated aqueous mixture, or it can be introduced with the silicone rubber monomers.
  • surfactants which can be used dodecylbenzenesulfonic acid is preferred.
  • Surfactants which can be used in the practice of the invention include acid catalyst-surfactants, for example, sulfonic acids, such as alkyl-, and alkaryl-arylsulfonic acids and mixtures of surface-active sulfonic acid salts with strong mineral acids. Additional sulfonic acid catalysts/surfactants are shown in U.S. Patent 3,294,725, and Craig, U.S. Patent 5,726,270 which are incorporated herein by reference.
  • silicone rubber monomers can be used to form the initial emulsion polymerized silicone rubber latex used in the practice of the invention.
  • Some of the preferred silicone rubber monomers include cyclosiloxanes, such as octamethylcyclotetrasiloxane, as shown for example in the Encyclopedia of Polymer Science and Engineering, Volume 15, 2nd Edition, pp. 205-308, (1989), John Wiley and Sons.
  • Cross-linking silanes include trifunctional such as trimethoxymethylsilane, and triethoxyphenyl- silane, and tetrafunctional, for example, tetraethoxysilane.
  • the cross-linking silanes can be used at from about 0.1% to 30% by weight of the silicone rubber monomer mixture.
  • Useful emulsion polymerizable silicone rubber monomers are for example cycloalkylsiloxanes, such as hexamethylcyclotrisiloxane, or octamethylcyclotetrasiloxane which can be copolymerized with from about 0.1% to about 30% by weight of a cross-linking agent.
  • Suitable cross-linking agents are for example, tetraalkoxysilane, such as, tetraethoxysilane, and in further combination with an alkylacryloxyalkyldialkoxyalkylsilane, as illustrated by ⁇ -methacryloxypropyldimethoxymethylsilane.
  • silicone rubber monomers A comprehensive list of silicone rubber monomers can be found in "Silicones”, Hardman and Torkelson, Encyclopedia of Polymer Science and Engineering, volume 15, 2nd Edition, pp. 205-308, (1989), John Wiley and Sons, which is incorporated herein by reference.
  • a suitable polymerizable alkenyl monomer alone, or in combination as a mixture of two or more alkenyl monomers, such as styrene, triallyl cyanurate, acrylonitrile, and methylmethacrylate, can be used in combination with the rubber latex.
  • styrene triallyl cyanurate
  • acrylonitrile acrylonitrile
  • methylmethacrylate a suitable polymerizable alkenyl monomer, alone, or in combination as a mixture of two or more alkenyl monomers, such as styrene, triallyl cyanurate, acrylonitrile, and methylmethacrylate.
  • their weight ratio is between about 90:10 to about 50:50.
  • the proportion of alkenyl monomer and emulsion polymerized rubber latex can vary widely by weight. For example, there can be used by weight, from about 15% to about 75% alkenyl monomer, based on the total weight of graft copolymer.
  • weight there can be used by weight, from about 15% to about 75% alkenyl monomer, based on the total weight of graft copolymer.
  • Weight percent solids of latex samples are determined after drying to a constant weight with a CEM Labwave 9000 gravimetric microwave drier. Particle size distributions are obtained using a Nicomp 370 Submicron Particle Sizer instrument applying a Gaussian analysis protocol.
  • a styrene and acrylonitrile mixture is pumped over a two hour period into a 5 liter glass reactor which contains an agitated mixture at 80°C of 1751 g of distilled water, and 1693 g of the above silicone rubber latex which has been neutralized to a pH of 6.5 with 4 g sodium bicarbonate dissolved in 50 ml water.
  • the styrene and acrylonitrile mixture consists of 573 g of styrene, 286 g of acrylonitrile, 1.3 g of a 75% sodium dioctylsulfosuccinate in 50/50 ethanol /water mixture, and 2.6 g t-amylperoxyoctoate.
  • the resulting reaction mixture is heated at 85°C for an additional two hours. The mixture is then allowed to cool to room temperature. There is obtained a silicone rubber graft copolymer latex.
  • the silicone rubber graft copolymer latex has 40.4% total solids by weight, and the volume average particle size is 741 nm.
  • the above graft copolymer latex is coagulated in a 1.5% aqueous calcium chloride solution maintained at 85°C, via slow addition of 1 part of the latex to two parts of calcium chloride solution.
  • the resulting polymer solids are filtered, washed with distilled water at ambient temperatures, and dried in a vacuum oven at room temperature for 24 hours, then at 70°C for at least 24 hours. There is obtained a fine powder.
  • the siloxane reactants are initially mixed under high shear conditions for 5 minutes at 8000 rpm. The mixture is then passed twice through a homogenizer for 2 passes under a pressure of 7000 psi to form a stable pre- emulsion. After stirring for 6 hours at 80°C, it is allowed to cool to room temperature to provide a silicone rubber latex having an average particle size of 240 nm.
  • This silicone rubber latex is grafted with a styrene and acrylonitrile following substantially the same procedure as shown above.
  • the resulting silicone rubber graft copolymer latex has 37% of total solids by weight.
  • An additional silicone rubber latex is prepared by constantly agitating a mixture of siloxane precursors for three hours at 89°C, followed by adding dropwise to the resulting mixture over three hours, a pre-emulsion of additional silicone rubber siloxane precursors. After post reacting for three hours, there is formed a silicone rubber latex having an average particle size of 170 nm. The resulting silicone rubber graft copolymer latex has 35% of total solids by weight.
  • Dry blends are prepared from the respective silicone-based graft copolymers based on respective silicone rubber latexes having an average particle size of 170 nm, 240 nm and 700 nm. There are used 54 parts of the silicone-based graft copolymer, 46 parts of a 75:25 by weight of a styrene- acrylonitrile copolymer, and 1 part Irganox 1076 stabilizer.
  • the respective dry blends are mixed and extruded to obtain pellets using a Welding Engineers 20 mm twin-screw extruder at 450°F set temperature, 400 rpm, and 15-17 lbs/hour throughput. The pellets are injected molded into test specimens using an Engel 30 ton injection molder with 450°F barrel set temperature and 145°F mold temperature.
  • Izod impact values are averages of six samples, specimen width 0.125 in, 2 lb pendulum capacity, obtained using a Testing Machines Inc. Monitor/Impact instrument model # 43-02 at room temperature.
  • thermoplastic materials are shown in the following Table where AN means styrene-acrylonitrile copolymer:
  • silicone latex made in accordance with the method of the present invention can provide impact modifiers which can be . used to make thermoplastic blends having enhanced impact strength and weatherability.
  • the impact modifiers of the present invention also can be used to impart improved impact strength and weatherability to other thermoplastic blends including those comprising at least one polyester, polycarbonate, polyestercarbonate, polyamide, polyimide, polyetherimide, polyphenylene ether, polystyrene, or a copolymer of styrene with acrylonitrile, methacrylonitrile, esters of acrylic acid, methacrylic acid or copolymers thereof.
  • Such impact modified blends are used in many applications requiring good weatherability and low temperature impact strength, including automotive, building, and construction applications, . and in articles of manufacture such as garden furniture, boats, signs, outdoor enclosures for electrical or telecommunications interface devices such as smart network interface devices (SNID), and the like.
  • SNID smart network interface devices

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)

Abstract

Cette invention se rapporte à un procédé servant à fabriquer du caoutchouc de silicone polymérisé en émulsion ayant une granulométrie moyenne comprise entre environ 400 nm et 2 microns, ainsi que des greffes de ce caoutchouc. Cette invention se rapporte également à des mélanges thermoplastiques ayant une meilleure résistance aux intempéries et une meilleure résistance aux chocs, sur la base de l'utilisation d'un polymère organique thermoplastique et d'une greffe d'un tel caoutchouc de silicone polymérisé en émulsion comme agent antichoc.
PCT/US1999/022870 1998-12-07 1999-10-04 Agents antichocs a base de caoutchouc de silicone polymerise en emulsion, procede de fabrication et melanges de ces agents WO2000034359A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2000586800A JP2002531654A (ja) 1998-12-07 1999-10-04 乳化重合シリコーンゴム系耐衝撃性改良剤、その製造方法並びにブレンド
DE69938462T DE69938462T2 (de) 1998-12-07 1999-10-04 Zähigkeitsvermittler aus emulsionspolymerisiertem silikonkautschuk, verfahren zu seiner herstellung und diesen enthaltende verbundwerkstoffe
EP99954707A EP1141093B1 (fr) 1998-12-07 1999-10-04 Agents antichocs a base de caoutchouc de silicone polymerise en emulsion, procede de fabrication et melanges de ces agents

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US20707398A 1998-12-07 1998-12-07
US09/207,073 1998-12-07

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WO2000034359A1 true WO2000034359A1 (fr) 2000-06-15
WO2000034359A9 WO2000034359A9 (fr) 2001-04-12

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US (2) US6433077B1 (fr)
EP (1) EP1141093B1 (fr)
JP (1) JP2002531654A (fr)
CN (1) CN1325537C (fr)
DE (1) DE69938462T2 (fr)
ES (1) ES2304067T3 (fr)
WO (1) WO2000034359A1 (fr)

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EP1186623A2 (fr) * 2000-09-11 2002-03-13 Dow Corning Corporation Emulsions anioniques et cathioniques de polysiloxanes
JP2003096142A (ja) * 2001-09-21 2003-04-03 Nippon A & L Kk グラフト重合体の製造方法及び耐衝撃性樹脂の製造方法
JP2003096141A (ja) * 2001-09-21 2003-04-03 Nippon A & L Kk 耐衝撃性改質剤の製造方法及び耐衝撃性樹脂の製造方法
CN100381484C (zh) * 2005-03-04 2008-04-16 华东理工大学 核壳型聚硅氧烷复合粒子的制备方法
WO2008130782A1 (fr) 2007-04-18 2008-10-30 Dow Global Technologies Inc. Polymères aromatiques de monovinylidène améliorés comprenant des polymères élastomères fonctionnalisés avec un sulfanylsilane
US7619010B2 (en) 2004-05-13 2009-11-17 Wacker Chemie Ag Method for the discontinuous production of silicone emulsions
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WO2004111125A1 (fr) * 2003-06-12 2004-12-23 Kaneka Corporation Composition de resine styrenique modifiee au caoutchouc
EP1871824B1 (fr) * 2005-03-24 2017-03-01 Bridgestone Corporation Compactage de caoutchouc renforce par silice, a faible emission de contaminants organiques volatils (cov)
US8501895B2 (en) * 2007-05-23 2013-08-06 Bridgestone Corporation Method for making alkoxy-modified silsesquioxanes and amino alkoxy-modified silsesquioxanes
US7915368B2 (en) 2007-05-23 2011-03-29 Bridgestone Corporation Method for making alkoxy-modified silsesquioxanes
US8962746B2 (en) * 2007-12-27 2015-02-24 Bridgestone Corporation Methods of making blocked-mercapto alkoxy-modified silsesquioxane compounds
US8513371B2 (en) * 2007-12-31 2013-08-20 Bridgestone Corporation Amino alkoxy-modified silsesquioxanes and method of preparation
US8794282B2 (en) 2007-12-31 2014-08-05 Bridgestone Corporation Amino alkoxy-modified silsesquioxane adhesives for improved metal adhesion and metal adhesion retention to cured rubber
CN102203170B (zh) 2008-08-29 2014-02-19 三菱丽阳株式会社 含有聚硅氧烷系聚合物的乙烯基聚合物粉体及其制造方法、树脂组合物以及成形体
US8642691B2 (en) 2009-12-28 2014-02-04 Bridgestone Corporation Amino alkoxy-modified silsesquioxane adhesives for improved metal adhesion and metal adhesion retention to cured rubber
WO2013162080A2 (fr) * 2013-08-13 2013-10-31 三菱レイヨン株式会社 Copolymère par greffage contenant un polyorganosiloxane, composition de résine, article moulé, agent d'amélioration des propriétés de glissement, et élément coulissant
CN114016318A (zh) 2014-12-31 2022-02-08 株式会社普利司通 用于将钢合金粘附到橡胶的氨基烷氧基改性倍半硅氧烷粘合剂
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Publication number Priority date Publication date Assignee Title
EP1186623A2 (fr) * 2000-09-11 2002-03-13 Dow Corning Corporation Emulsions anioniques et cathioniques de polysiloxanes
EP1186623A3 (fr) * 2000-09-11 2003-07-02 Dow Corning Corporation Emulsions anioniques et cathioniques de polysiloxanes
JP2003096142A (ja) * 2001-09-21 2003-04-03 Nippon A & L Kk グラフト重合体の製造方法及び耐衝撃性樹脂の製造方法
JP2003096141A (ja) * 2001-09-21 2003-04-03 Nippon A & L Kk 耐衝撃性改質剤の製造方法及び耐衝撃性樹脂の製造方法
US7619010B2 (en) 2004-05-13 2009-11-17 Wacker Chemie Ag Method for the discontinuous production of silicone emulsions
CN100381484C (zh) * 2005-03-04 2008-04-16 华东理工大学 核壳型聚硅氧烷复合粒子的制备方法
WO2008130782A1 (fr) 2007-04-18 2008-10-30 Dow Global Technologies Inc. Polymères aromatiques de monovinylidène améliorés comprenant des polymères élastomères fonctionnalisés avec un sulfanylsilane
GB2460586A (en) * 2007-04-20 2009-12-09 Gen Instrument Corp Simulating short depth of field to maximize privacy in videotelephony

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DE69938462T2 (de) 2009-01-15
EP1141093A1 (fr) 2001-10-10
ES2304067T3 (es) 2008-09-01
DE69938462D1 (de) 2008-05-15
US6433077B1 (en) 2002-08-13
CN1325537C (zh) 2007-07-11
EP1141093B1 (fr) 2008-04-02
US20020188063A1 (en) 2002-12-12
JP2002531654A (ja) 2002-09-24
WO2000034359A9 (fr) 2001-04-12
CN1329630A (zh) 2002-01-02

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